1. Technical Field
The present invention relates to a method for the manufacture of photosensitizing nanomaterials and products thereof and the use of the photosensitizing nanomaterials in photodynamic treatment to inactivate a biological target.
2. Background Art
The manufacture of a photosensitizing metal complex bound to a nanomaterial is known in the art.
Japanese Patent Publication Number JP-A-2007/196104, which is titled “Zeolite material including complex and its utilisation”, is assigned to The Nayoga Institute of Japan. The JP-A-2007/196104 disclosure teaches a zeolite solid support including a complex containing a metal of groups 1-13 of the periodic table and an oxygen activation metal complex included in a unit cell of the zeolite solid support and a photosensitizing metal complex retained (preferably included in the unit cell of the zeolite solid support) on the zeolite solid support. The metal contained in the zeolite solid support is for example, at least one of silver, copper, zinc, platinum and palladium. The oxygen activation metal complex is for example, a metal phthalocyanine complex synthesised in the unit cell of the zeolite solid support.
The '104 disclosure does not teach the attachment of a Si(IV) tetrapyrrole metal complex that is covalently bonded directly to the surface of a solid support. The '104 disclosure fails to teach the use of silica nanoparticles as the nanomaterial. There is no disclosure pertaining to the use of the manufactured products for the photodynamic treatment of biological targets.
Japanese Patent Publication Number JP-A-62-104807 is titled “Macromolecular metal complex” and the applicant is Shirai Hiroyashi of Nippon Carbide Kogyo KK, Nittesu KK, Earth Clean KK. The '807 disclosure teaches a metal complex with a high odour-decomposition rate and with outstanding persistency when used as a deodorant. The metal complex is manufactured by bonding a macromolecular compound to a metal phthalocyanine derivative to form an oxidative and reductive metal complex. The macromolecular metal complex can be obtained by bonding to a macromolecular compound (e.g., polystyrene, poly-vinyl alcohol) a metal phthalocyanine derivative containing peripheral substituents, where the central atom M is an oxidative or reductive metal atom (M can be manganese, cobalt, nickel or iron, the substituents can be carbonyl chloride or acetaldehyde). The metal complex is used by dissolution or dispersion in water or an organic liquid, or by adsorption to a zeolite solid support.
The '807 disclosure does not teach the attachment of a Si(IV) tetrapyrrole metal complex covalently bonded directly to the surface of a zeolite L nanomaterial. The '807 disclosure fails to teach the use of silica nanoparticles as the nanomaterial. There is no disclosure in this '807 document pertaining to the use of the manufactured product for the photodynamic treatment for biological targets.
Japanese Patent Publication Number JP-A-2007-231247 is titled “Method for producing phthalocyanine compound pigment micro-particle, phthalocyanine compound pigment micro-particle obtained by the same, ink-jet ink for colour filter, colouring photosensitive resin composition and photosensitive resin transfer material comprising the same and colour filter, liquid crystal display device and CCD device using the same”. The applicant of this '247 disclosure is Fuji Film Corp. The '247 disclosure discloses a method for producing a phthalocyanine compound pigment of micro-particles of nanometer size, the micro-particles having excellent dispersion stability and fluidity and achieving high contrast and weather resistance, to provide an inkjet ink for a colour filter, a colouring photosensitive resin composition and a photosensitive resin transfer material comprising the same and to provide the colour filter, a liquid crystal display device and a CCD device (charge coupled device) using the same. The method for producing the phthalocyanine compound pigment micro-particle is achieved as follows. A pigment solution is prepared by dissolving a phthalocyanine compound pigment in a good solvent and mixing with a solvent compatible with the good solvent and providing a poor solvent for the pigment to deposit and produce the pigment and thus prepare a dispersion of the pigment micro-particle of nanometer size. In the process, a high polymer having a mass-average molecular weight ≧1,000 is contained in the dispersion of the pigment micro-particle.
This '247 disclosure teaches pigment micro-particles which consist of phthalocyanine which is not covalently attached to a nanomaterial. The '247 disclosure does not teach the use of the active pigment micro-particles for the photodynamic treatment of biological targets.
One article in the academic journal, Eur. J. Inorg. Chem., 2008, 2975 is titled “Synthesis and photo physical properties of silica-gel supported photo functional (phthalocyaninato) silicon complexes”, describes the synthesis and photo physical properties of the silica-gel supported photosensitizing phthalocyaninato silicon complex (SiPc-SiO2). The photo physical properties and surface structures of the silica-gel supported photosensitizing phthalocyaninato) silicon complex (SiPc-SiO2) were investigated in terms of their electronic absorption, fluorescence, singlet (1O2) oxygen luminescence, and nitrogen adsorption-desorption isotherms. The nitrogen adsorption-desorption isotherms indicate that the planes of SiPcs anchored by axial ligands are parallel to the silica gel surface. In the proposed structure the tetradentate phthalocyaninato (Pc) ligands are considered to coordinate with the silica-gel particles, since the central elements of the SiPcs, such as Si—O—Si—OH, are similar to constituents of the silica-gel. The intensities of fluorescence and singlet oxygen luminescence decrease with an increase in the amount of SiPcs due to interactions between the SiPcs aggregates. By changing the amount of SiPcs, solid materials are prepared based on Pc complexes with both monomeric photo physical properties and a high ability for singlet oxygen generation. The electronic absorption spectrum of the photosensitive (phthalocyaninato) silicon complex (SiPc-SiO2) indicate that a wide optical window is maintained between the Soret and Q absorption bands, even at high concentrations of SiPcs i.e. [SiPc]≈10−2 M. This results in deep green solids, which is unlike the blue colour of the crystals or concentrated solutions (>10−5 M) of SiPc(OH)2.
The Eur. J. Inorg. Chem. disclosure does not teach the attachment of a Si(IV) tetrapyrrole metal complex with a covalent bond to the surface of a zeolite L nanomaterial. The Eur. J. Inorg. Chem. disclosure also fails to teach the use of silica nanoparticles as the nanomaterial. There is no disclosure in the Eur. J. Inorg. Chem. publication pertaining to the use of the photosensitizing phthalocyaninato silicon complex (SiPc-SiO2) in photodynamic therapy.